Prepared resin



Dec. 15, 1931. c. A. THOMAS ET AL PREPARED RES IN Filed July 21, 1928 1N VENTOR Patented Dec. 15, 1931 UNITED STATES PATENT OFFICE CHARLES A. THOMAS AND CARROLL A. HOCHWALT, 0F DAYTON, OHIO, ASSIGHORS, BY MESNE ASSIGNMENTS, TO DAYTON SYNTHETIC CHEMICALS, INQ, OF DAYTON, OHIO,

A CORPORATION OF OHIO PREPARED RESIN Application filed July 21, 1928. Serial No. 294,491.

This invention relates to the preparation of substances analogous in character and utility to the so-called natural resins; and one of the principal objects of this invention is to provide such a prepared substance which has characteristics markedly superior, in certain respects to the natural resins, and a method of, and apparatus for, preparing such substances.

Other objects and advantages of the present invention will be apparent from the description thereof set out below and from the drawing and appended claims.

The single view of the drawing is a diagrammatic representation of apparatus for practicing the method, and for producing the resin-like material of the invention.

The term resin has heretofore been generally utilized to designate certain naturally formed compounds, such as shellac, amber, the hardened product exuding from pine trees and known as rosin, and the like. These compounds have been long used in the arts, particularly in connection with the preparation of varnishes, lacquers and the like. Such compounds, when suitably dissolved and admixed with other proper constituents, go to produce these varnishes, lacquers, etc. However, the utilization of these natural resins has always presented a problem because the resin tends to retard the drying of linseed oil which is present in large quantities in varnish, etc. and also because they are saponifiable and so are attacked by acids. We have discovered that the prepared resins of our invention are free from these objectionable characteristics. They are non-acid in reaction and also they are unsaponifiable.

In the practicing of our invention to produce these prepared resins we preferably utilin an abundantly available product, name ly cracked distillate such as that obtained from natural gas. Distillate cracked according to the various methods now prevalent, contains a substantial proportion of unsaturated hydrocarbons, .theproportion, with respect to the total quantlty of distillate, being dependent upon the method utilized in the cracking. While many of the cracked distillates ordinarily available will not include more than 4 or 5 per cent of these unsaturated hydrocarbons it is not at all unusual for fuel available on the market for use in automobiles to have an unsaturated content of 20 or perhaps 25per cent. And by utilizing a sufliciently severe crackingprocess distillate. can be secured having in excess of 50 per cent of unsaturated hydrocarbons. These unsaturated h drocarbons are of course of uncontrolled character, in the sense that such hydrocarbons form according to the conditions of the reaction, in respect to any particular batch of distillate being treated. And consequently in the prac-- ticing of our method of producing prepared resins, we utilize an indeterminate mixture of unsaturated'h drocarbons, which may be of any possible c araoter.

This unsaturated distillate is, preferably first topped, by which we mean it is subjected to a rather rough or crude fractional distillation, to separate therefrom a portion consisting of a mixture of the lighter hydrocarbons. Very satisfactory results have been secured using a topped fraction having an end point of approximately 180 C. or. less. This topped distillate is placed within the container or agitating chamber 10, which is in turn enclosed within a suitable water jacket 11, through which water may be flowed for either coollng or heating the container 10, and the material therein, to maintain a proper temperature range for the reaction to occur. Valve controlled inlet and outlet pipes 12 through which cooling or heating water may be introduced into the water jacket are shown. Of course any usual form of heat-controlled jackets may be utilized.

The container 10 is provided with a removable or detachable. cover or top .15 which may be tightly clamped in position. This top carries a motor 16, mounted in any suitable fashion, the shaft 17 of which projects downwardly into the container and carries a suitable stirrer or agitator 18 upon the lower end. Leading ofi' through the top from the interior of chamber 10 is a reflux v condenser coil 20, positioned within a suitable cooling jacket 21 to which cooling liquid may be introduced through the valve com the loss of the. generated vapors and due building up of pressures during the reao inlet 22 and discharged through the valvgcontrolled discharge 23. The upper end of th s condenser may be open, as the purpose 'of itiis merely to condense and return to the container 10 any vapors that may be generat-.

both

ed during the reaction, thus prevent tions. The thermometer 24 is provided so that the temperature within the container may be quickly checked. The unsaturated distillate, such as cracked asolin'e, is introduced into the container rou a supply 30, controlled b a suitab Gl Yfll -VG 31.

his pipe may lea to any suitable source of supply. of distillate.- The top 15 is 'provided with a port, which is shown as being closed up b means of a removable plug 32, through which an activating com ound, such as pulverized anhydrous aluminum chloride (141 01,) is added to the unsaturated distillate within the container.

The aluminum chloride is added insmall quantities at a time. Presuming, for example, that 4,000 cc. of cracked distillate having approximately 50 per cent of unsaturate hydrocarbons is introduced into container 10,

anhydrous aluminum chloride may be satisthe temperature to rise from normal temperature, of say 23 C. to ap roximatel C., which temperature has een 'found to give a ver satisfactory end product. If necessary t e jacket 11 may be utilized to maintain this temperature. aluminum chloride are added from time to time as may be done without unduly increasing the temperature within container 10 until no additional temperature rise results.

The amount of aluminum chloride used will depend upon the proportion of unsaturated hydrocarbons, and perhaps upon their character, and therefore it is a very satisfactory ractice to add'aluminum chloride until no urther temperature rise is secured. Inasmuch as the aluminum is ultimately recovered the addition inexcess is not a detriment.

With 4,000 cc. of a 50 percent unsaturated distillate as referred to above, it will ordinarilytake approximately 50 grams to complete the conversion of the unsaturated compounds.

It should be stated that in addition to aluminum chloride other com unds which hyrolyze in water giving an aci reaction will Additional batches of function satisfactorily cause theconversion ofthe unsaturated hydrocarbons into resins ,.for example, chlorides of iron, boron,

zinc, antimony, indium, titanium and tin;

benzene sulfomc acid;- ropyl alcohol satu rated with HOl as; ethyl sulfate, and aniline hydrobromicfia. v

When the conversion within the container 10 has been com leted the material within I the container be a viscous dark-colored one. This material is flowed from the container through the outlet pipe 35 -controlled 7 by a suitable valve 36 into a steam distillation vessel or container. 40. This particular part of the apparatus is shown 1n afvery diagrammatic character and ma be of widely varying character. As shown t e viscous reaction product is flowed into the container 40 to'the' desired height. This'container has a steam inlet pipe 41, controlled by a suitable valve-.42.. The container is provided with a removable top 43 carryin a motor operated stirrer 43'. and a distillatlon discharge pi 44 which leads to a condenser coil 45 within a suitable condenser jacket 46, through which cooling water may be introduced through vlalve-controlled pipe 47 and discharged t ro beginning of th'esteammg action an excess over the theoretical amount of a water soluh valve-controlled pipe 48. Steam is intro need through the pipe 41. Also at the tion of. alkali required to neutralize all of p the aluminum chloride previously utilized by introduction into the container10 is passed into the distillation vessel 40; preferabl about twice the theoretical amount is use This can be introduced through any desired apparatus, the drawing showin the ipe 41 as rovided with a valve branc 50 t lo lll ih which the alkali may be introduced. e

agitator 43" is then started in order to stir up the reaction mass and secure efiective admixture with the neutralizing agent, and to secure more effective steam distillation.

Various water soluble alkalies might be used,-

but preferably sodium hydroxide or ammonium hydroxide, which will permeate all through the mass 'of reaction product and therefore function effectively to neutralize all of the aluminum compound. During this portion of the treatment the almuinum chloride and alkali, such as sodium hydroxide, in the presence of water will react to form aluminum hydroxide (Al (OH) and sodium chloride (NaCl). j'

During this steaming action the saturated, or other hydrocarbons, which have not been affected by the aluminum chloride, will be,

distilled off, and will pass off along with the steam through the pipe 44 and be condensed, the condensed water and recovered hydrocarbons being collected in any suitable container shown diagrammatically as a closed. vessel 51. While treatment by the introduction of steam is described above it is not essential, it being only needful that the reaction product be treated with a compound containing a hydroxyl radical such as water to decompose the aluminum chloride. But since the unacted upon hydrocarbons should be distilled off at this stage preferably steam or boiling water is used.

During the steaming, the reaction product within the vessel 40 changes color and becomes first green and then a putty color, in

fact looking very much like white putty. During this chan e the saturated hydrocarbons, and some of the heavier oils occluded within the viscous mass, are driven off. The white or putty color is apparently due to the finely divided aluminum hydroxide particles and sodium chloride particles which are disreaction product and tributed through the 2 will not come out during the steaming action;

and to occluded water. 5

After the steaming action is completed, which will ordinarily take several hours, the putty-like product is removed from the vassel and treated with a hydrocarbon solvent, preferably benzol, although other suitable solvents which are immiscible in water, such as carbon tetrachloride and ethylene dichloride, may be used. The putty-like product 8 may be removed from the vessel 40 by heating until the mass is molten when it may be discharged through the outlet pipe 55 controlled by a valve 56. For this purpose the vessel 40 is provided with a steam jacket 57 having controlled steam inlet and outlet connections 58 and 59. Preferably the puttylike mass is first treated in the hydrocarbon solvent, such as benzol, which is introduced into the vessel 40 by the valve-controlled inlet pipe 60, the vessel being heated by the steam jacket and stirred with agitator 43 to effect solution of the resin in the benzol. When so dissolved a colloidal mass is produced, the resin like compounds going into solution in the benzol and the aluminum hydroxide and water forming the colloidal portion.-

The colloidal mass is flowed by gravity through the out-let pipe 55 into an open vessel 62 equipped with a suitable stirrer such as an electric stirrer having agitating blades 63 driven by an electric motor 64. A water soluble liquid, or one which is miscible with water in all pro ortions, and which is active to precipitate the resin, such as alcohol or acetone, is then added to the benzol solution through the supply pipe 65 controlled by a valve 66. Generally a volume of alcohol which is equivalent to about twice the volume of the colloidal solution is added. This serves to precipitate the prepared resin compound, the mass separating out into two layers 67 and 68. The lower layer 68 comprises the precipitated resin and the aluminum hydrox- 65 ide and sodium chloride. The upper layer addition of comprises a mixture of benzol and alcohol together with some dissolved higher oils which remain in solution in the benzol, and water which is taken up in the alcohol. The contents of vessel 62 are agitated during the the alcohol, and then are allowed to settle or stratify into the two layers above described.

The layers are then separated in any suitable manner such as by decantin Prefer-- ably the lower layer is flowed by gravity through a passage 70 controlled by a valve 71 into another vessel 72. The alcohol and benzol mixture is then withdrawn .for reclaiming purposes or for use through the discharge pipe 73 controlled by a valve 74.

If it is desired to reclaim and separate the alcohol and benzol, this may be readily accomplished by adding a quantity of water to the mixture, when the benzol wi 1 separate in a layer distinct from a mixed alcohol and water layer, when they may be separated by decanting. The resin now in the vessel 72 is in a semi-solid form. The vessel 72 is provided with a tight fitting cover 76 and with a reflux condenser 77 to condense any volatile products and return them to the vessel 72 as well as to prevent any undue pressure rise therein. The vessel 72 is also provided with a steam jacket 78 having valve-controlled steam inlet and outlet connections 79 and 80, as Well as with a benzol or other hydrocarbon solvent inlet pipe 81 controlled by a valve 82. Benzol is then added to the semisolid resin in the vessel 72 and the same is heated by the steam jacket to effect solution of the resin therein. In the absence of Water which has been removed by the alcohol in the previous treatment, a granular precipitate is formed which can be readily filtered. Sodium chloride remaining in the mass also remains in the precipitate.

In the appended claims, for the sake of brevity, the term activating agent is used to refer to the activating agent in its initial form, as for example, anhydrous aluminum chloride; and the term precipitated activating agent is used to refer to decomposition products of such activating agent which are precipitated during the process as herein described.

The precipitate is removed by filtering in any suitable manner such as through a chamois filter press or in a centrifuge. As shown, the liquid mass and precipitate is flowed through the discharge pipe 85 controlled by valve 86 into a filter press 87 illustrated diagrammatically. The filtrate including the purified resin dissolved in benzol passes through the valve controlled pipe 90 into a distillation vessel 91 having a close fitting cover 92 and a distillation cit-take pipe 93 leading to a condenser 94. The vessel 91 is also provided with a steam jacket 95 having valve controlled steam inlet and outlet connections 96 and 97. Vessel 91 is then heated by the steam jacket which serves to distill off the benzol and any occluded water remaining in the mass, the benzol bein condensed by the condenser 94 and recovered in a vessel illustrated dia ammatically at 98. Immediately after the distillation and while the resin is still molten, it is flowed by gravity through the discharge ipe 99 into a shallow pan 100, or into a p uralit of such shallow pans, where the resin is a lowed to cool and harden. While any suitable form of feed from one vessel to another of the sys: tem may be provided, a ravity feed through out the entire system S1151 as disclosed herein is preferred for commercial installations.

The resin obtained is rather soft due to the presence of some higher oils. If hard resin, free from the higher oils is desired, the resin may be again p aced in a. hydrocarbon solvent such as benzol and relprecipitated by alcohol or acetone, the hig er olls-remaining -insolution in the benzol and alcohol mix ture. This solution mixture may be separated by decanting the two' formed layers in the manner above described, and the precipitate may then be heated under vacuum which drives off all alcohol and benzol, and a clear brittle resin results.

The resin so prepared in accordance with our invention is found to have a brown shading to dark amber color. When dissolved in a suitable oil solvent, such as na htha, the resin forms a clear amber liquid, w ich when brushed onto a surface leaves a clear film which is practically colorless or has only a faint yellowish color. A characteristic feature of this prepared resin is its high molecular weight. The molecular weight, particularly when treated with the activating agent athigher temperatures (about 40 (1.), is generally over 1300 and often approaches 1500. The prepared resin is non-acid in reaction, and is unsaponifiable. Another very important and desirable characteristic of the prepared resin is that it does not retard the drying of linseed oil, so that a varnish can be prepared with this resin which compares favorably in speed of drying with lacquers. The term cracked distillate is herein used to denote distillate obtained in the process of cracking petroleum and natural gas as distinguished from coal tar distillate, such as that commonly known as solvent naphtha, and which has been employed to produce resins of the coumarone-indene type, the constituents of which are largely aromatic in character. The cracked distillate employed in the present invention is of quite different character, being largel aliphatic in character and substantially ree from coumaroneindene constituents.

While the method herein described and the apparatus for carrying out that method a and the products so p'roduoed constitute preferred embodiments of our invention it is to be understood that the invention is not limited to this precise method or apparatus, or precise product, and that changes may be made therein without departing from the scope of the invention which is defined in the ap ended claims.

at is claimed is:

1. As a. composition of matter, a highly polymerized hard pulverizable synthetic resin produced from cracked petroleum distillate, substantially completely soluble at all stages of polymerization in benzol and asoline and substantially completely insolu le in alcohol and acetone, the resin being substantially non-acid, unsaponifiable and a non-retarder of the drying of linseed oil.

2. As a composition of matter, a resinous reaction product formed by inter-reaction and polymerization in the presence of a metallic halide activatin agent, of a mixture of unsaturated hydrocar on compounds of varying degrees of unsaturation and having boiling points below 180 (3., consisting of a substantial number of the members of the group of hydrocarbons present in a fraction of cracked petroleum distillate, said resinous reaction product being substantially completely soluble in benzol and naphtha, substantially free from halides and capable of being hardened to a ulverizable amorphous solid as distinguished from a soft and elastic caoutchouc-like material.

3. A new composition of matter comprising the homogeneous resinous reaction product formed in the presence of a metallic halide activating agent from the unsaturated hydrocarbon compounds havin boilin points below. 180 C. present in a Fraction 0? cracked etroleum distillate, said resinous product eing substantially completely insoluble in alcohol and acetone and substantially completely soluble in benzol and naphtha.

4. A solid substantiall neutral amber colored resin comprising t e reaction roduct of a mixture of unsaturated hydrocar ons of varying degrees of unsaturation consisting of a substantial number of the members of the group of hydrocarbons present in a fraction of cracked petroleum distillateand substantially free from coumarone-indene constituents, formed in the presence of a metallic halide activating agent, said resin being substantially freefrom metal and halogen compounds, substantially completel' insoluble in alcohol and acetone, and capab e of formin a clear light colored solution in benzol am naphtha.

5. A solid substantially neutral amber colored resin formed from a fraction of cracked petroleum distillate, said resin being substantially completely soluble in benzol and asoline and substantially completely inso uble in alcohol and acetone.

6. The method of producing prepared resins, which comprises agitating with a metallic halide activating agent added in chemically uncombined form, a mixture of unsaturated hydrocarbons of Varying degrees of unsaturation consisting of a substantial number of the members of the group of hydrocarbons present in cracked petroleum distillate, introducing steam into the reaction product to decompose and precipitate the metallic halide activating agent, and separating the precipitated activating agent from the resinous reaction product.

7. The method of producing prepared resins which comprises agitating a fraction of cracked petroleum distillate and a metallic halide activating agent added insolid form in successive controlled amounts to produce a resinous reaction product admixed with heavy oils, adding to the resulting mass an alkali to neutralize the activating ent with decomposition and precipitation of the activating a ent, adding to the reaction mass a solvent or the resinous reaction product in which the precipitated activating agent is insoluble, se arating the precipitated activating agent rom the solution of resinous product, heating the solution to separate the resinous product from the solvent, and further heating the resinous product to remove remaining heavy oils and harden the resinous reaction product.

8. The method in the production of pre pared resins which comprises as steps thereof polymerizing a fraction of cracked petroleum distillate substantially free from coumarone-indene constituents, with a metallic halide which hydrolyzes to give an acid reaction, added in solid form, and neutralizmg the reaction product with an alkaline ammonium compound.

9. The method of producing prepared resins which comprises reacting a mixture of unsaturated hydrocarbon compounds conslsting of a substantial number of the members of the group of hydrocarbons present in a fraction of cracked petroleum distillate, said hydrocarbons having boiling oints below 180 C. and being substantially free from coumarone-indene constituents, in the presence of a metallic halide activating agent added in chemically uncombined form, adding to the reaction mixture water which acts as a splitting agent tobreak down and precipitate the activating agent, adding to the resultant mass a solvent for the resinous reaction product, and separating the precipitated activating agent from the resinous reaction product after such addition of solvent.

10. A method in the production of a syn- .thetic resin which comprises reacting a mixgroup of hydrocarbons present in cracked petroleum distillate, with a metallic halide activating agent which gives an acid reaction in water, addedin a chemically uncombined state, neutralizing the reaction mixture with ammonia in the presence of water to break down and precipitate the metallic halide activating agent, and separating the precipitated activating agent from the dissolved resinous reaction product.

11. The method in the production of a synthetic resin which comprises as a step thereof treating a petroleum cracked distillate fraction containing in excess of 40% by weight of unsaturated hydrocarbons with a metallic halide activating agent added in solid form in sufiicient amount to produce substantially complete polymerization of resin-forming constituents.

12. The method in the production of a synthetic resin which comprises as a step thereof reacting a cracked petroleum distillate fraction containing in excess of 50% by weight of a mixture of unsaturated hydrocarbons of varying degrees of unsaturation having boiling points below 180 C. in the presence of a metallic halide activating agent added in a chemically uncombined state.

13. The method of producing a synthetic resin which comprises as steps thereof adding a metallic halide activating agent in solid form in successive controlled amounts with agitation to a mixture of a substantial number of the unsaturated hydrocarbons present in a fraction of cracked petroleum distillate, while cooling the reaction mass to prevent a temperature rise above 60 0., and continuing the addition of the metallic halide until substantially no further'temperature rise due to the exothermic heat of reaction takes place.

14. The method of producing a synthetic resin which comprises as a step thereof reacting a fraction of cracked petroleum distillate substantially free from coumaroneindene constituents and containin more than 50% of unsaturated hydrocar ons, in the presence of more than 1% by weight of anhydrous aluminum chloride, added in a chemically uncombined state.

In testimony whereof we hereto afiix our signatures.

CHARLES A. THOMAS. CARROLL A. HOCHWALT. 

